JP3921763B2 - Method for forming bismuth titanate film - Google Patents
Method for forming bismuth titanate film Download PDFInfo
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- JP3921763B2 JP3921763B2 JP32293797A JP32293797A JP3921763B2 JP 3921763 B2 JP3921763 B2 JP 3921763B2 JP 32293797 A JP32293797 A JP 32293797A JP 32293797 A JP32293797 A JP 32293797A JP 3921763 B2 JP3921763 B2 JP 3921763B2
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- bismuth
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- bismuth titanate
- titanium oxide
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Description
【０００１】
【発明の属する技術分野】
本発明は、コンデンサ、圧電素子、焦電センサ、強誘電性メモリ等に利用しうるチタン酸ビスマス被膜の製造方法に関するものである。
【０００２】
【従来の技術】
従来より、チタン酸ビスマス被膜は産業上有用な物質であり、コンデンサ、圧電素子、焦電センサ、強誘電性メモリ等への応用が検討されている。
【０００３】
このようなチタン酸ビスマス被膜の形成方法は、スパッタリング法、真空蒸着法、ＣＶＤ法などの乾式成膜法や、スプレイパイロリシス法、ゾル−ゲル法、液相成長法などの湿式成膜法により基体上に成膜することが試みられている。
【０００４】
【発明が解決しようとする課題】
しかしながら、従来のスパッタリング法、真空蒸着法、ＣＶＤ法などの乾式成膜法では、成膜装置が大掛かりで高価であり、また成膜可能な基体面積が制限される、組成や膜厚制御が難しい、複雑な形状には成膜が難しい等の欠点がある。
【０００５】
またスプレイパイロリシス法、ゾル−ゲル法、液相成長法などの湿式成膜法においても、数百度の高温加熱が必要となるため、耐熱性の弱い基板は使用できず、基板加熱用の機器が必要になり使用環境も限られてくるという問題があった。
【０００６】
【課題を解決するための手段】
本発明者らは、上述の技術的問題点に鑑みて鋭意研究を重ねた結果、基体上にチタン酸化物被膜を形成した後に、該チタン酸化物被膜をビスマス塩および過酸化物を含む水溶液中で陽極酸化することにより、大掛かりな装置を必要とせず、大面積かつ複雑形状の基体上にも、膜厚および組成の均一なチタン酸ビスマス被膜を容易に得られる方法を見出し、本発明を完成するに至った。
【０００７】
すなわち本発明は、基体上にチタン酸化物被膜を形成する工程と、前記チタン酸化物被膜をビスマス塩および過酸化物を含む水溶液中で陽極酸化する工程とを含むことを特徴とする。
【０００８】
本発明の製造方法における基体上のチタン酸化物被膜の形成方法には、特に限定はない。例えば、スパッタリング法、真空蒸着法、ＣＶＤ法などの乾式成膜法、ゾル−ゲル法、電解析出法などの湿式成膜法で形成したものを用いることができる。このうち、電解析出法によるものが、成膜プロセスの低温下、容易さ、使用装置の低価格化等の観点から望ましい。
【０００９】
また、使用するビスマス塩としても特に限定はない。例えば、臭化ビスマス、塩化ビスマス、くえん酸ビスマス、よう化ビスマス、硝酸ビスマス、りん酸ビスマス、オキシ塩化ビスマス等が使用できる。さらに、ビスマス金属、酸化ビスマス、水酸化ビスマス等を酸性溶液中で溶解させたものも使用できる。
【００１０】
使用する過酸化物も、特に限定はない。例えば、過酸化水素、ペルオキソ硝酸、ペルオキソ一硫酸、ペルオキソ二硫酸、ペルオキソ一硫酸ナトリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ一硫酸カリウム、ペルオキソ二硫酸カリウム、ペルオキソ一炭酸ナトリウム、ペルオキソ一炭酸カリウム、ペルオキソ二炭酸ナトリウム、ペルオキソ二炭酸カリウム、ペルオキソ一りん酸、ペルオキソ二りん酸、ペルオキソ一りん酸ナトリウム、ペルオキソ二りん酸ナトリウム、ペルオキソ一りん酸カリウム、ペルオキソ二りん酸カリウム、ペルオキソほう酸、ペルオキソほう酸ナトリウム等が使用できる。このうち、チタン酸ビスマス被膜への不純物の混入を少なくできる点や入手しやすい点などから、過酸化水素水を使用することが好都合である。
【００１１】
本発明において、ビスマス塩、過酸化物は、それぞれ一種類のものを用いてもよいし、複数のものを混合して用いても良い。なお、ビスマス塩は含むが過酸化物を含まない溶液を用いた場合には、チタン酸化物の溶解が起こりチタン酸ビスマス被膜は得られないことが後述の比較実験から判明している。
【００１２】
ビスマス塩および過酸化物の濃度は広い範囲で使用可能であるが、低濃度すぎるとチタン酸化物の溶解のみが生じるためチタン酸ビスマス被膜は得られず、また高濃度すぎるとビスマス酸化物のみの生成となる傾向がある。このため通常、ビスマスイオンおよび過酸化物イオンのそれぞれの濃度が、０．００１ｍｏｌ／Ｌ〜１．０ｍｏｌ／Ｌ程度の範囲にあることが適当であり、特にそれぞれの濃度が０．１ｍｏｌ／Ｌ程度であることが好ましい。
【００１３】
また、ビスマス塩および過酸化物を含む水溶液の水温も、広い範囲で設定可能であるが、通常は２０℃〜１００℃程度が適当であり、５０℃〜８０℃程度が好ましい。さらに、水溶液のｐＨ範囲も広い範囲で設定可能であるが、ｐＨ８〜１４の範囲であればよく、特にｐＨ１０〜１３程度とすることが好ましい。この際、ｐＨ３以上の水溶液では、ほとんどのビスマス塩が加水分解し溶液が白濁してしまうため、場合によってはビスマス錯体形成が必要である。この場合に使用する錯化剤としては特に限定はなく、例えばエチレンジアミン四酢酸塩、ニトリロ酢酸塩等が挙げられる。これらの錯化剤は、一種類で用いても良いし、複数のものを混合して用いても良い。
【００１４】
さらに、チタン酸化物被膜を形成する基体に特に限定はない。例えば、銅、ニッケル、白金、金、ステンレス鋼、チタンなどの金属材料、あるいは導電性セラミックス材料、導電性ガラス材料等が挙げられる。また、各種の絶縁体基体上に前述の導体を形成したものを用いても良い。基体は、陽極酸化を行う前に表面改質、エッチング等の前処理を行っても良い。
【００１５】
加えて、結晶性の向上、膜欠陥の補正、結晶変態等の観点から、本発明によってチタン酸ビスマス被膜を作製したのちに、熱処理を施すことも可能である。
【００１６】
本発明において、チタン酸化物被膜の形成された基体を陽極酸化する方法としては、通常の陽極酸化法がいずれも採用できる。例えば、三極式の電解セルを形成装置として用いた場合、作用電極電位は溶液中のビスマス塩および過酸化物濃度に応じて設定可能であるが、通常Ａｇ／ＡｇＣｌ電極基準で＋０．５〜＋６．０Ｖ程度が適当であり、＋１．０〜＋５．０Ｖ程度が好ましい。
【００１７】
【発明の実施の形態】
以下、本発明に従って実施した実験について説明する。なお、薬品はすべて試薬特級（ナカライテスク（株）製）を使用した。チタン酸ビスマス被膜作成用基体（すなわち作用電極）としてはｓｕｓ３０４（ニラコ（株）製）を用い、常法に従い脱脂処理を行った。また、電解セルは通常用いられている三極式のもの（対電極：Ｐｔ箔２０×３０×０．１ｍｍ、高純度化学（株）製、参照電極：飽和ＫＣｌ入りＡｇ／ＡｇＣｌ、堀場製作所（株）製、セル容量：３００ｍＬ）を使用した。
【００１８】
【実験例１】
まず、先に準備したｓｕｓ３０４上に、高周波スパッタリング法により膜厚０．５μｍのチタン酸化物被膜を形成した。この際、ターゲットとして二酸化チタン（純度９９．５％、高純度化学（株）製）を、形成時の雰囲気ガスとしてアルゴンガス（純度９９．９９９％、住友精化（株）製）を用い、チャンバー内真空度３．０×１０-3Ｔｏｒｒ、投入電力量３００Ｗの条件とした。
【００１９】
次に、電解セルに下記の組成のチタン酸ビスマス被膜作成用水溶液を入れたあと、恒温槽中にセットしたのち、以下の条件下で陽極酸化を行った。
【００２０】
塩化ビスマス ０．１ ｍｏｌ／Ｌ
クエン酸三ナトリウム塩 ０．４ ｍｏｌ／Ｌ
過酸化水素水（３０重量％過酸化水素含有） ０．１ ｍｏｌ／Ｌ
（２０重量％水酸化ナトリウム水溶液でｐＨ１１まで調整）
上記水溶液中で、液温を６０℃に保持し、＋２．０Ｖ、９０分で陽極酸化を行ったところ、陽極酸化前には無色透明であったチタン酸化物被膜が薄暗い黄色に着色された。この膜をＸ線回折法により測定したところ、チャートには結晶性チタン酸ビスマスおよびチタン金属箔に起因するピークが認められた。
【００２１】
【実験例２】
先に準備したｓｕｓ３０４上に、電解析出法により膜厚０．４μｍのチタン酸化物被膜を形成した。この際、チタン酸化物被膜作成用の電解液には、三塩化チタン、クエン酸、硝酸カリウム、過酸化水素をいずれも０．０１ｍｏｌ／Ｌ含むｐＨ６．０の水溶液を用いた。
【００２２】
次に、電解セルに下記の組成のチタン酸ビスマス被膜作成用水溶液を入れたあと、恒温槽中にセットしたのち、以下の条件下で陽極酸化を行った。
【００２３】
硝酸ビスマス ０．１ ｍｏｌ／Ｌ
ニトリロ酢酸塩 ０．４ ｍｏｌ／Ｌ
ペルオキソほう酸ナトリウム ０．１ ｍｏｌ／Ｌ
（２０重量％水酸化ナトリウム水溶液でｐＨ１２まで調整）
上記水溶液中で、液温を７０℃に保持し、＋３．０Ｖ、６０分で陽極酸化を行ったところ、陽極酸化前には無色透明であったチタン酸化物被膜が薄暗い黄色に着色された。この膜を、実験例１と同様に、Ｘ線回折法により同定したところチタン酸ビスマスであった。
【００２４】
【実験例３】
チタン酸化物被膜は、実験例２と同様の条件で、電解析出法によりｓｕｓ３０４上に形成した。
【００２５】
次に、電解セルに下記の組成のチタン酸ビスマス被膜作成用水溶液を入れたあと、恒温槽中にセットしたのち、以下の条件下で陽極酸化を行った。
【００２６】
クエン酸ビスマス ０．０５ ｍｏｌ／Ｌ
エチレンジアミン四酢酸二ナトリウム塩 ０．２ ｍｏｌ／Ｌ
ペルオキソ二硫酸ナトリウム ０．０５ ｍｏｌ／Ｌ
（２０重量％水酸化ナトリウム水溶液でｐＨ１０まで調整）
上記水溶液中で、液温を５０℃に保持し、＋４．０Ｖ、６０分で陽極酸化を行ったところ、陽極酸化前には無色透明であったチタン酸化物被膜が薄暗い黄色に着色された。この膜を、実験例１と同様に、Ｘ線回折法により同定したところチタン酸ビスマスであった。
【００２７】
【比較例】
チタン酸化物被膜は、実験例１と同条件で、高周波スパッタリング法によりｓｕｓ３０４上に形成した。
【００２８】
次に、電解セルに過酸化物を除いた下記の組成のチタン酸ビスマス被膜作成用水溶液を入れたあと、恒温槽中にセットしたのち、以下の条件下で陽極酸化を行った。
【００２９】
塩化ビスマス ０．０５ ｍｏｌ／Ｌ
エチレンジアミン四酢酸二ナトリウム塩 ０．２ ｍｏｌ／Ｌ
（２０重量％水酸化ナトリウム水溶液でｐＨ１０まで調整）
上記水溶液中で、液温を５０℃に保持し、＋３．０Ｖ、６０分で陽極酸化を行った。この陽極酸化の間に、ｓｕｓ３０４上に形成されていたチタン酸化物被膜の一部が剥離する現象が観察された。陽極酸化後、ｓｕｓ３０４上の膜を、実施例１と同様に、Ｘ線回折法により同定したところ、チタン酸ビスマスに起因するピークは見られず、チタン金属箔に起因するピークのみが認められた。
【００３０】
【発明の効果】
このように本発明によれば、基体上にチタン酸化物被膜を形成したのちに、該被膜をビスマス塩および過酸化物を含む水溶液中で陽極酸化することにより、大掛かりな装置を必要とせず、大面積および複雑形状の基体上にも、膜厚および組成が均一なチタン酸ビスマス被膜を容易に得ることが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a bismuth titanate film that can be used for capacitors, piezoelectric elements, pyroelectric sensors, ferroelectric memories, and the like.
[0002]
[Prior art]
Conventionally, bismuth titanate coating is an industrially useful substance, and its application to capacitors, piezoelectric elements, pyroelectric sensors, ferroelectric memories and the like has been studied.
[0003]
Such a bismuth titanate film can be formed by a dry film formation method such as a sputtering method, a vacuum evaporation method, or a CVD method, or a wet film formation method such as a spray pyrolysis method, a sol-gel method, or a liquid phase growth method. Attempts have been made to form a film on a substrate.
[0004]
[Problems to be solved by the invention]
However, in conventional dry deposition methods such as sputtering, vacuum deposition, and CVD, the deposition apparatus is large and expensive, and the substrate area on which the film can be formed is limited, and it is difficult to control the composition and film thickness. The complicated shape has drawbacks such as difficulty in film formation.
[0005]
Also, wet deposition methods such as the spray pyrolysis method, sol-gel method, and liquid phase growth method require heating at a high temperature of several hundred degrees, so that a substrate with low heat resistance cannot be used. There is a problem that the use environment is limited.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above technical problems, the present inventors have formed a titanium oxide film on a substrate, and then formed the titanium oxide film in an aqueous solution containing a bismuth salt and a peroxide. A method for easily obtaining a bismuth titanate film with a uniform film thickness and composition on a large-area, complex-shaped substrate was found without the need for a large-scale apparatus, and the present invention was completed. It came to do.
[0007]
That is, the present invention includes a step of forming a titanium oxide film on a substrate and a step of anodizing the titanium oxide film in an aqueous solution containing a bismuth salt and a peroxide.
[0008]
There is no limitation in particular in the formation method of the titanium oxide film on a base | substrate in the manufacturing method of this invention. For example, a film formed by a dry film formation method such as a sputtering method, a vacuum evaporation method, or a CVD method, or a wet film formation method such as a sol-gel method or an electrolytic deposition method can be used. Among these, the electrolytic deposition method is desirable from the viewpoints of the low temperature and ease of the film forming process, the cost reduction of the equipment used, and the like.
[0009]
Further, the bismuth salt used is not particularly limited. For example, bismuth bromide, bismuth chloride, bismuth citrate, bismuth iodide, bismuth nitrate, bismuth phosphate, bismuth oxychloride and the like can be used. Furthermore, what melt | dissolved bismuth metal, bismuth oxide, bismuth hydroxide, etc. in the acidic solution can also be used.
[0010]
The peroxide to be used is not particularly limited. For example, hydrogen peroxide, peroxonitric acid, peroxomonosulfuric acid, peroxodisulfuric acid, sodium peroxodisulfate, sodium peroxodisulfate, potassium peroxomonosulfate, potassium peroxodisulfate, sodium peroxomonocarbonate, potassium peroxomonocarbonate, peroxodicarbonate Sodium, potassium peroxodicarbonate, peroxomonophosphate, peroxodiphosphate, sodium peroxomonophosphate, sodium peroxodiphosphate, potassium peroxomonophosphate, potassium peroxodiphosphate, peroxoborate, sodium peroxoborate, etc. it can. Among these, it is advantageous to use a hydrogen peroxide solution because it can reduce the amount of impurities mixed into the bismuth titanate film and is easily available.
[0011]
In the present invention, as the bismuth salt and the peroxide, one kind each may be used, or a plurality of kinds may be mixed and used. It has been found from a comparative experiment described later that when a solution containing a bismuth salt but not containing a peroxide is used, the titanium oxide is dissolved and a bismuth titanate film cannot be obtained.
[0012]
The concentration of bismuth salt and peroxide can be used in a wide range. However, if the concentration is too low, only the dissolution of titanium oxide occurs, so that a bismuth titanate film cannot be obtained. Tend to generate. For this reason, it is usually appropriate that the respective concentrations of bismuth ions and peroxide ions are in the range of about 0.001 mol / L to 1.0 mol / L, and in particular each concentration is about 0.1 mol / L. It is preferable that
[0013]
The water temperature of the aqueous solution containing the bismuth salt and peroxide can also be set in a wide range, but is usually about 20 ° C to 100 ° C, and preferably about 50 ° C to 80 ° C. Furthermore, the pH range of the aqueous solution can be set in a wide range, but it may be in the range of pH 8 to 14, and is preferably about pH 10 to 13. At this time, in an aqueous solution having a pH of 3 or more, most of the bismuth salt is hydrolyzed and the solution becomes cloudy. Therefore, in some cases, it is necessary to form a bismuth complex. The complexing agent used in this case is not particularly limited, and examples thereof include ethylenediamine tetraacetate and nitriloacetate. These complexing agents may be used alone or as a mixture of a plurality of them.
[0014]
Furthermore, there is no particular limitation on the substrate on which the titanium oxide film is formed. For example, metal materials such as copper, nickel, platinum, gold, stainless steel, and titanium, conductive ceramic materials, conductive glass materials, and the like can be given. Moreover, you may use what formed the above-mentioned conductor on various insulator base materials. The substrate may be subjected to pretreatment such as surface modification and etching before anodizing.
[0015]
In addition, from the viewpoint of improvement in crystallinity, correction of film defects, crystal transformation, and the like, it is also possible to perform heat treatment after producing a bismuth titanate film according to the present invention.
[0016]
In the present invention, as a method for anodizing a substrate on which a titanium oxide film is formed, any ordinary anodizing method can be employed. For example, when a triode type electrolysis cell is used as a forming device, the working electrode potential can be set according to the bismuth salt and peroxide concentration in the solution, but is usually +0.5 to the Ag / AgCl electrode standard. About +6.0 V is appropriate, and about +1.0 to +5.0 V is preferable.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, experiments conducted according to the present invention will be described. All chemicals used were reagent grade (Nacalai Tesque). As a substrate for forming a bismuth titanate film (that is, a working electrode), sus304 (manufactured by Niraco Co., Ltd.) was used, and degreasing treatment was performed according to a conventional method. In addition, the electrolysis cell is a commonly used tripolar type (counter electrode: Pt foil 20 × 30 × 0.1 mm, manufactured by High Purity Chemical Co., Ltd., reference electrode: Ag / AgCl with saturated KCl, Horiba ( Co., Ltd., cell capacity: 300 mL) was used.
[0018]
[Experiment 1]
First, a 0.5 μm-thick titanium oxide film was formed on the previously prepared sus 304 by high-frequency sputtering. At this time, titanium dioxide (purity 99.5%, manufactured by High Purity Chemical Co., Ltd.) was used as a target, and argon gas (purity 99.999%, manufactured by Sumitomo Seika Co., Ltd.) was used as an atmospheric gas during formation. The conditions were such that the degree of vacuum in the chamber was 3.0 × 10 −3 Torr and the input power was 300 W.
[0019]
Next, an aqueous solution for forming a bismuth titanate film having the following composition was placed in the electrolytic cell, and after setting in a thermostatic bath, anodic oxidation was performed under the following conditions.
[0020]
Bismuth chloride 0.1 mol / L
Trisodium citrate salt 0.4 mol / L
Hydrogen peroxide solution (containing 30 wt% hydrogen peroxide) 0.1 mol / L
(Adjusted to pH 11 with 20% by weight aqueous sodium hydroxide)
In the above aqueous solution, the liquid temperature was kept at 60 ° C. and anodization was performed at +2.0 V for 90 minutes. As a result, the colorless and transparent titanium oxide film before the anodization was colored dim yellow. When this film was measured by an X-ray diffraction method, peaks attributable to crystalline bismuth titanate and titanium metal foil were observed on the chart.
[0021]
[Experimental example 2]
A titanium oxide film having a thickness of 0.4 μm was formed on the previously prepared sus 304 by electrolytic deposition. At this time, an aqueous solution having a pH of 6.0 containing 0.01 mol / L of titanium trichloride, citric acid, potassium nitrate, and hydrogen peroxide was used as the electrolytic solution for forming the titanium oxide film.
[0022]
Next, an aqueous solution for forming a bismuth titanate film having the following composition was placed in the electrolytic cell, and after setting in a thermostatic bath, anodic oxidation was performed under the following conditions.
[0023]
Bismuth nitrate 0.1 mol / L
Nitriloacetate 0.4 mol / L
Sodium peroxoborate 0.1 mol / L
(Adjusted to pH 12 with 20 wt% sodium hydroxide aqueous solution)
In the above aqueous solution, the temperature of the solution was kept at 70 ° C., and anodization was performed at +3.0 V for 60 minutes. As a result, the colorless and transparent titanium oxide film before the anodization was colored dim yellow. When this film was identified by the X-ray diffraction method as in Experimental Example 1, it was bismuth titanate.
[0024]
[Experiment 3]
The titanium oxide film was formed on sus304 by electrolytic deposition under the same conditions as in Experimental Example 2.
[0025]
Next, an aqueous solution for forming a bismuth titanate film having the following composition was placed in the electrolytic cell, and after setting in a thermostatic bath, anodic oxidation was performed under the following conditions.
[0026]
Bismuth citrate 0.05 mol / L
Ethylenediaminetetraacetic acid disodium salt 0.2 mol / L
Sodium peroxodisulfate 0.05 mol / L
(Adjusted to pH 10 with 20 wt% sodium hydroxide aqueous solution)
In the above aqueous solution, the liquid temperature was kept at 50 ° C. and anodization was performed at +4.0 V for 60 minutes. As a result, the titanium oxide film, which was colorless and transparent before the anodization, was colored dim yellow. When this film was identified by the X-ray diffraction method as in Experimental Example 1, it was bismuth titanate.
[0027]
[Comparative example]
The titanium oxide film was formed on sus304 by the high frequency sputtering method under the same conditions as in Experimental Example 1.
[0028]
Next, after putting an aqueous solution for forming a bismuth titanate film having the following composition in the electrolytic cell excluding the peroxide, it was set in a thermostatic bath and then anodized under the following conditions.
[0029]
Bismuth chloride 0.05 mol / L
Ethylenediaminetetraacetic acid disodium salt 0.2 mol / L
(Adjusted to pH 10 with 20 wt% sodium hydroxide aqueous solution)
In the aqueous solution, the liquid temperature was maintained at 50 ° C., and anodization was performed at +3.0 V for 60 minutes. During this anodic oxidation, a phenomenon was observed in which a part of the titanium oxide film formed on the sus 304 was peeled off. After anodization, the film on sus304 was identified by X-ray diffraction as in Example 1. As a result, no peak due to bismuth titanate was observed, and only a peak due to titanium metal foil was observed. .
[0030]
【The invention's effect】
Thus, according to the present invention, after forming the titanium oxide film on the substrate, the film is anodized in an aqueous solution containing a bismuth salt and a peroxide, so that a large-scale apparatus is not required. It is possible to easily obtain a bismuth titanate film having a uniform film thickness and composition even on a substrate having a large area and a complicated shape.
Claims (3)
前記チタン酸化物被膜を、ビスマス塩および過酸化物を含む水溶液中で陽極酸化する工程と、
を含むことを特徴とするチタン酸ビスマス被膜の形成方法。Forming a titanium oxide film on the substrate;
Anodizing the titanium oxide film in an aqueous solution containing a bismuth salt and a peroxide;
A method for forming a bismuth titanate film, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP32293797A JP3921763B2 (en) | 1997-11-25 | 1997-11-25 | Method for forming bismuth titanate film |
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| Application Number | Priority Date | Filing Date | Title |
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| JP32293797A JP3921763B2 (en) | 1997-11-25 | 1997-11-25 | Method for forming bismuth titanate film |
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| Publication Number | Publication Date |
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| JPH11158692A JPH11158692A (en) | 1999-06-15 |
| JP3921763B2 true JP3921763B2 (en) | 2007-05-30 |
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| JP4803550B2 (en) * | 2006-03-07 | 2011-10-26 | 地方独立行政法人 大阪市立工業研究所 | Composition for electrolytic formation of silver oxide film |
| WO2009108286A1 (en) * | 2008-02-28 | 2009-09-03 | Corning Incorporated | Electrochemical methods of making nanostructures |
| CN104131308A (en) * | 2014-07-24 | 2014-11-05 | 青岛农业大学 | Preparation method for bismuth tungstate |
| RU2614916C1 (en) * | 2016-04-05 | 2017-03-30 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for bismuth titanate thin layers production |
| CN114216949B (en) * | 2021-11-18 | 2023-08-08 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
| CN114457358B (en) * | 2022-01-18 | 2023-04-25 | 安徽大学 | Bi/TiO 2 Series electrocatalytic material and its preparation method and application |
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